Photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern formation method

Abstract

Provided is a photosensitive resin composition comprising: (A) a silicone resin having an epoxy group and/or a phenolic hydroxyl group; (B) a photoacid generator represented by formula (B); and (C) a carboxylic acid quaternary ammonium compound.

1 . A photosensitive resin composition comprising
 (A) a silicone resin containing an epoxy group and/or phenolic hydroxy group,   (B) a photoacid generator having the formula (B):   
       
         
           
           
               
               
           
         
         wherein R A  is a C 1 -C 12  hydrocarbyl group in which some or all hydrogen may be substituted by fluorine and some —CH 2 — may be replaced by a carbonyl group, 
         R B  is each independently a monovalent organic group, two or more R B  may bond directly or via —O—, —S—, —SO—, —SO 2 —, —NH—, —CO—, —COO—, —CONH—, a C 1 -C 20  saturated hydrocarbylene group or phenylene group, to form a ring structure containing element E, 
         E is an n-valent element selected from Groups 15 to 17 in the Periodic Table, and n is an integer of 1 to 3, and 
         (C) a carboxylic acid quaternary ammonium compound. 
       
     
     
         2 . The photosensitive resin composition of  claim 1  wherein the silicone resin (A) has the formula (A): 
       
         
           
           
               
               
           
         
         wherein R 1  to R 4  are each independently a C 1 -C 8  hydrocarbyl group, k is an integer of 1 to 600, a and b indicative of the compositional ratio (or molar ratio) of corresponding repeat unit are numbers in the range: 0<a<1, 0<b<1, and a+b=1, and X is a divalent organic group containing an epoxy group and/or phenolic hydroxy group. 
       
     
     
         3 . The photosensitive resin composition of  claim 2  wherein the silicone resin (A) comprises repeat units having the formulae (a1) to (a4) and (1) to (b4): 
       
         
           
           
               
               
           
         
         wherein R 1  to R 4  are each independently a C 1 -C 8  hydrocarbyl group, k is an integer of 1 to 600, a 1  to a 4  and b 1  to b 4  indicative of the compositional ratio (or molar ratio) of corresponding repeat unit are numbers in the range: 0≤a 1 <1, 0<a 2 <1, 0≤a 3 <1, 0≤a 4 <1, 0≤b 1 <1, 0≤b 2 <1, 0≤b 3 <1, 0≤b 4 <1, 0<a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1, X 1  is a divalent group having the following formula (X1), X 2  is a divalent group having the following formula (X2), X 3  is a divalent group having the following formula (X3), X 4  is a divalent group having the following formula (X4), 
       
       
         
           
           
               
               
           
         
         wherein Y 1  is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 11  and R 12  are each independently hydrogen or methyl, R 13  and R 14  are each independently a C 1 -C 4  saturated hydrocarbyl or C 1 -C 4  saturated hydrocarbyloxy group, p 1  and p 2  are each independently an integer of 0 to 7, q 1  and q 2  are each independently an integer of 0 to 2, the broken line designates a valence bond, 
       
       
         
           
           
               
               
           
         
         wherein Y 2  is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 21  and R 22  are each independently hydrogen or methyl, R 23  and R 24  are each independently a C 1 -C 4  saturated hydrocarbyl or C 1 -C 4  saturated hydrocarbyloxy group, r 1  and r 2  are each independently an integer of 0 to 7, s 1  and s 2  are each independently an integer of 0 to 2, the broken line designates a valence bond, 
       
       
         
           
           
               
               
           
         
         wherein R 31  and R 32  are each independently hydrogen or methyl, t 1  and t 2  are each independently an integer of 0 to 7, the broken line designates a valence bond, 
       
       
         
           
           
               
               
           
         
         wherein R 41  and R 42  are each independently hydrogen or methyl, R 43  and R 44  are each independently a C 1 -C 8  hydrocarbyl group, u 1  and u 2  are each independently an integer of 0 to 7, v is an integer of 0 to 600, and the broken line designates a valence bond. 
       
     
     
         4 . The photosensitive resin composition of  claim 1 , wherein E is sulfur and n is 2. 
     
     
         5 . The photosensitive resin composition of  claim 1 , further comprising (D) a crosslinker. 
     
     
         6 . The photosensitive resin composition of  claim 5  wherein the crosslinker (D) is at least one compound selected from a nitrogen-containing compound selected from melamine, guanamine, glycoluril and urea compounds, having on the average at least two methylol and/or alkoxymethyl groups in the molecule, an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on the average at least two methylol or alkoxymethyl groups in the molecule, and an epoxy compound having on the average at least two epoxy groups in the molecule. 
     
     
         7 . The photosensitive resin composition of  claim 1 , further comprising (E) a solvent. 
     
     
         8 . A photosensitive resin coating obtained from the photosensitive resin composition of  claim 1 . 
     
     
         9 . A photosensitive dry film comprising a support and the photosensitive resin coating of  claim 8  thereon. 
     
     
         10 . A pattern forming process comprising the steps of:
 (i) applying the photosensitive resin composition of  claim 1  onto a substrate to form a photosensitive resin coating thereon,   (ii) exposing the photosensitive resin coating to radiation, and   (iii) developing the exposed resin coating in a developer to form a pattern of the resin coating.   
     
     
         11 . A pattern forming process comprising the steps of:
 (i′) using the photosensitive dry film of  claim 9  to form the photosensitive resin coating on a substrate,   (ii) exposing the photosensitive resin coating to radiation, and   (iii) developing the exposed resin coating in a developer to form a pattern of the resin coating.   
     
     
         12 . The pattern forming process of  claim 10 , further comprising (iv) post-curing the patterned resin coating resulting from the development step at a temperature of 100 to 250° C. 
     
     
         13 . The photosensitive resin composition of  claim 1 , which is a material adapted to form a coating for protecting electric and electronic parts. 
     
     
         14 . The photosensitive resin composition of  claim 1 , which is a material adapted to form a substrate-bonding coating for bonding two substrates.